101 years of superconductivity

Kazimierz Conder
Laboratory for Developments and
Methods, Paul Scherrer Institute,
5232 Villigen PSI, Switzerland

kazimierz.conder@psi.ch

Resistivity

Electrical resistivity at low temperatures

Kelvin: Electrons will be frozen
resistivity grows till .

Kelvin (1902)

Matthiessen (1864)
Dewar (1904)

Temperature

Dewar: the lattice will be

frozen the electrons will not
be scattered. Resistivity wiil
decrese till 0.
Matthiesen: Residual resistivity
because of contamination and
lattice defects.

One of the scientific challenge at the end of 19th

and beginning of the 20th century: How to reach
temperatures close to 0 K?
Hydrogen was liquefied (boiling point 20.28 K)
for the first time by James Dewar in 1898

Superconductivity- discovery I
1895 William Ramsay in England
discovered helium on the earth
1908 H. Kamerlingh Onnes liquefied
helium (boiling point 4.22 K)
Resistivity at low temperatures- pure
mercury (could repeatedly distilled
producing very pure samples).
Repeated resistivity measurements indicated zero resistance at the liquid-helium
temperatures. Short circuit was assumed!
During one repetitive experimental run, a young technician fall asleep. The helium
pressure (kept below atmospheric one) slowly rose and, therefore, the boiling
temperature. As it passed above 4.2 K, suddenly resistance appeared.

Hg TC=4.2K

From: Rudolf de Bruyn Ouboter, Heike Kamerlingh Onness

Discovery of Superconductivity, Scientific American March 1997

Superconductivity- discovery II
Liquid Helium (4K)
(1908). Boiling point
4.22K.
Superconductivity in
Hg TC=4.2K (1911)

Mercury has passed into a new state,

which on account of its extraordinary

electrical properties may be called the
superconducting state
H. Kamerlingh Onnes 1913 (Nobel preis 1913)

Resistivity R=0 below TC;

(R<10-23 cm, 1018 times
smaller than for Cu)

Further discoveries
1911-1986: Low temperature
superconductors Highest TC=23K
for Nb3Ge
1986 (January): High Temperature
Superconductivity (LaBa)2 CuO4
TC=35K
K.A. Mller und G. Bednorz (IBM
Rschlikon) (Nobel preis 1987)
1987 (January): YBa2Cu3O7-x TC=93K
1987 (December): Bi-Sr-Ca-Cu-O TC=110K,
1988 (January): Tl-Ba-Ca-Cu-O TC=125K
1993: Hg-Ba-Ca-Cu-O TC=133K
(A. Schilling, H. Ott, ETH Zrich)

140

HgBa2Ca2Cu3O8
Tl2Sr2Ca2Cu3O10

120

Bi2Sr2Ca2Cu3O10

TC [K]

100

YBa2Cu3O7

Liquid nitrogen

80
60

La2-xSrxCuO4

40
20
Hg

Pb

1920

Nb

NbN

1940

Nb3Ge

Nb3Sn
NaxWO3
NbO

1960
Year

MgB2

Cs2RbC60
Ba1-xKxBiO3

BaPb1-xBixO3

1980

LHe

2000
6

Zero resistivity
Low temperatures:
LN2 -1960C (77K)

The current can flow 100 000

years!!
7

Meissner-Ochsenfeld-effect
A superconductor is a perfect
diamagnet. Superconducting
material expels magnetic flux from
the interior.
W. Meissner, R. Ochsenfeld (1933)
On the surface of a superconductor
(T<TC) superconducting current will
be induced. This creates a magnetic
field compensating the outside one.

Screening (shielding ) currents

Magnetic levitation

Superconducting elements

Ferromagnetic elements are not superconducting

The best conductors (Ag, Cu, Au..) are not superconducting
Nb has the highest TC = 9.2K from all the elements
9

Classical model of superconductivity

1957 John Bardeen, Leon Cooper, and John Robert Schrieffer

An electron on the way through the lattice interacts with lattice

sites (cations). The electron produces phonon.

During one phonon

oscillation an electron can
cover a distance of ~104.
The second electron will
be attracted without
experiencing the repulsing
electrostatic force .

The lattice
deformation
creates a region
of relative
positive charge
which can attract
another electron.

10

Nobel Prize in Physics

1972
"for their jointly developed
theory of superconductivity,
called the BCS-theory
John Bardeen, Leon Neil Cooper, John Robert Schrieffer

eCoherence
length

Phonon

Cooper pair model

e-

Fermie und Bose-Statistic

Energy

Energy

Density of states

Fermions- elemental particles

with 1/2 spin (e.g. electrons,
protons, neutrons..)
Pauli-Principle every energy
level can be occupied with
maximum two electrons with
opposite spins.

Density of states

Cooper-Pairs are created with

electrons with opposite spins.
Total spin of C-P is zero. C-P are
bosons. Pauli-Principle doesnt
obey.
All C-P can have the same
quantum state with the same
energy.
12

Creation of a C-Pairs diminishes

energy of electrons. Breaking a
pair (e.g. through interaction
with impurity site) means
increase of the energy.

A movement of the C-P when a

supercurrent is flowing, is
considered as a movement of a
centre of the mass of two
electrons creating C-P.

eAll the C-P are in the same quantum

state with the same energy. A
scattering by a lattice imperfection
(impurity) can not change quantum
state of all C-P at the same time
(collektive behaviour).

Phonon

e-

BCS Theory: some consequences

Good electrical conductors
are showing no
superconductivity
In case of good conductors is the
interaction of carriers with the
lattice very week. This is, however,
important for superconductivity.

Isotope effect
The Cooper-Pairs are created
(glued) by the electron-phonon
interaction. Energy of the phonons
(lattice vibrations) depends on the
mass of the lattice site .
Superconductivity (Tc) should
depend on the mass of the ions
(atoms) creating the lattice.

TC~M-
For most of the lowtemperature
superconductors =0.5

14

What destroys superconductivity?

A current: produces magnetic field which in turn
destroys superconductivity.
Current density

Temperature
Magnetic field

Magnetic field: the spins of the C-P

will be directed parallel.

High temperatures: strong

thermal vibration of the
lattice predominate over
the electron-phonon
coupling.

(should be antiparallel in C-P)

15

Coherence length
Concentration C-P
Superconductor

SL
SC

(Xi)
I

x<

SC
SL
GL

Coherence length is the

largest insulating distance
which can be tunneled by
Cooper-Pairs.

GL

Coherence length is the distance

between the carriers creating a
Cooper-Pair.
16

Nobel Prize in Physics 1973

"for his theoretical predictions of the properties of
a supercurrent through a tunnel barrier, in
particular those phenomena which are generally
known as the Josephson effects".

Brian David Josephson

The superconducting tunnel Josephson)

junction (superconductorinsulator
superconductor tunnel junction (SIS)
is an electronic device consisting of two
superconductors separated by a very thin
layer of insulating material

Josephson discovered in
1963 tunnelling effect being
23-years old PhD student

SL
SC

SL
SC

x< GL

Superconductor

Eindringtiefe

Penetration
depth

Penetration depth

0
depicts the distance where
B(x) is e-time smaller than on the
surface

4 -0.5

(T)=0*(1-(T/TC) )

TC

Temperatur
Temperature

18

Ginzburg-Landau Parameter =/ GL
<1/2=0.71 Superconductor Type I

Al
Sn
Pb

Tc

[nm] [nm]

1.2
3.7
7.2

16
34
37

0.01
0.16
0.4

1600
230
83

>0.71 Superconductor Type II

Nb
Nb3Sn
YBa2Cu3O7
Rb3C60

Bi2Sr2Ca2Cu3O10

Tc

[nm] [nm]

9.3
18
93
30
110

39
80
150
247
200

1
27
100
124
19
143

38
3
1.5
2.0
1.4

Superconductor type I (/ GL<0.71) in a magnetic field

The field created on the
surface of the superconductor
compensating the outside field

Bi=Ba+ 0M
Outside field

Inside field Bi

Magnetization 0M

The field inside the

superconductor

Outside field Ba

Superconductor
Bi=0

Negative units !

Outside field Ba

Normal
conductor Bi=Ba

20

Superconductor type II in a magnetic field

Meissner
phase

Mixed
phase

Outside field Ba

Normal
conductor

Average inside field Bi

Magnetization 0M

Bi=Ba+ 0M

Outside field Ba

Vortex-lattice in
superconductor type II.
Magnetic flux of a vortex is
quantized:
0=h/2e2.0710-15Tm2
21

Magnetic induction B

Superconductor type II. B-T-Diagram

Normal state

Mixed phase
Meissner
phase

Temperature T

STM (Scanning Tunneling

Microscopy). Abrikosov-lattice
in NbSe2
H. Hess, R.B. Robinson, and J.V. Waszczak,
Physica B 169 (1991) 422
22

Nobel Prize in Physics

2003
"for pioneering
contributions to the theory
of superconductors and
superfluids".
Alexei A. Abrikosov, Vitaly L. Ginzburg, Anthony J. Leggett

Type I

Type II

24

Perovskite ABX3
X

X=O2-, F-, Cl-)

A=alkali, alkali-earth and rareearth metals,
B=transition metals (also Si, Al,
Ge, Ga, Bi, Pb)

Perovskite is named for a Russian

mineralogist, Count Lev Aleksevich
von Perovski. The mineral (CaTiO3)
was discovered and named by Gustav
Rose in 1839 from samples found in
the Ural Mountains.
25

High Temperature Superconductor. La2-xSrxCuO4

(LaBa)2 CuO4 TC=35K K.A. Mller und G.
Bednorz (IBM Rschlikon 1986 )
Cu

10
0.0

TC

Metal

TN

Insulator

100

Antiferromagnet

La, Sr

Temperature [K]

La2-xSrxCuO4

Superconductor

0.1
0.2
0.3
Sr-content x, (holes per CuO2-layer)

2SrO 2SrLa + 2OxO + VO

VO+ 0.5O2 OxO+ 2h

26

High Temperature Superconductor: YBa2Cu3O7-x

BaO

CuO2 layer

5-fold Cu
coordination
CuO-chain
4-fold Cu
coordination

Perovskite
YBa2Cu3O9

27

Oxygen doping in YBa2Cu3O7-x

TC

YBa2Cu3O7-

80
60
40

Superconductor

20

6.2

6.4

6.6

6.8

Oxygen content (7-)

Oxygen content depends

on temperature and
oxygen partial pressure

7.0

Thermogavimetry
7.0

100.0

YBa2Cu3O6.985

6.8

99.5

6.6

99.0

98.5

6.4
200

400

600

800

1000

Temperature [ C]

28

Oxygen index

0
6.0

Weight [%]

Temperature [K]

100

Layered structure of YBa2Cu3O7-x

CuO

BaO
CuO2
Y

Conducting CuO2 layers

Charge reservoir

Conducting CuO2 layers

holes
electrons
holes

2Cu2+ + 0.5O2 2Cu3+ +O22CuxCu + V O +0.5O2 2CuCu + OxO

2CuCu 2CuxCu + 2h
29

Layered structure of YBa2Cu3O7-x. Anisotropy

Unit cell

Cooper-pairs can not tunnel through

the charge reservoir!
3.4

YBa2Cu3O7
ab []

8.3

1500

c []
6000

TC=93

ab []

c []

15

Bi2Sr2Ca2 Cu3O10 TC=110

ab []

c []

2000

10 000

ab []

c []

13

For YBa2Cu3O7 single crystals at 4.2K

jc(ab)~107A/cm2, jc(c)~105A/cm2
30

Bi-Sr-Ca-Cu-O
C a
C a

BiO
BiO
SrO
CuO2

C a

C a

Ca

C a
C a

Bi2Sr2CuO6 2201
TC=20K

Bi2Sr2CaCu2O8 2212
TC=95K

Bi2Sr2Ca2Cu3O10 2223
TC=110K
31

HgBa2Can-1CunO2n+2 Hg-12(n-1)n

CuO2-layers
World record 133K !!!
ETH Zrich - A.Schilling, M.Cantoni, J.D.
Guo, H.R.Ott, Nature, 362(1993)226

TC fr HgBa2Can-1CunO2n+2
Hg-12(n-1)n

Temperature [K]

140
130
120
110
100
90
1
2
3
4
5
6
7
Number of CuO2-layers in the unit
32 cell

Magnetic ion in the structure

Sm

TC=55K

April, 2008

33

Cs0.8(FeSe0.98)2

FeSe
Intercalation

K0.8(FeSe0.98)2

Cs0.8(FeSe0.98)2

Cs

Crystal growth in Cs (or K)- vapour in

quartz ampoules at 1050oC

New superconductor Lix(C5H5N)yFe2-zSe2

Synthesized via intercalation of dissolved alkaline metal (Li)
in anhydrous pyridine at room temperature.

C5H5N

Synthesis of a new alkali metal-organic solvent intercalated

iron selenide superconductor with Tc45K
A. Krzton-Maziopa, E. V. Pomjakushina, V. Yu. Pomjakushin, F.
von Rohr, A. Schilling, K. Conder

arXiv:1206.7022

USO
USO

Unidentified Superconducting Object

36

Applications. Wires and bands.

Abfllen in
Silberrhrchen
und Schweissen

Extrusion

Extrusion
c ab

Walzen und Erhitzen bei

800-900oC

37
American Superconductor

Applications. Wires and bands.

Cross section of HTC

band
American Superconductor
Corporation

HTC Cable
38

Application. Industry.
Magnetic bearing

A flywheel in a vacuum chamber energy

accumulator.

MagLev train
(magnetic levitation)

SMES: Superconducting
Magnetic Energy
Storage
Saves energy in form of
magnetic field produced
by a superconducting
coil.
39

Summary

History of discovery and farther development

How it works (still open problem for HTc)
What are the materials
Potential applications

A spin of a Cooper pair is:

1
1/2
2

Most of the HTc superconductors are:

Cuprates

Nickelates

Cobaltates

Manganates

Superconductors type II in comparison to type I:

have shorter coherence length
and longer penetration depth

have shorter coherence length

and shorter penetration depth

are cuprates (all other

superconductors are type I)

have longer coherence length

and shorter penetration depth

In the BCS theory it is assumed that the interaction between electrons in Cooper pairs is
mediated by:
photons

Coulomb force

phonons

magnetic interaction

Vortex phase is observed:

For all superconductors type I

Only in cuprates

For all superconductors above

Tc

For all superconductors type II

Isotope effect (Tc dependence on lattice mass) is:

a proof of BCS theory
(electron-phonon interaction)

a proof that superconductor is

of type II

only observed for hole doped

superconductors

not observed in
superconductors

In case of many High Temperature superconductors in order to achieve temperatures

below Tc one can use:
Ice+water

Liquid nitrogen

Dry ice (solid CO2sublimation at 78.5 C)

No cooling is necessary